Determination of antibiotics of the tetracycline group in water by high-performance liquid chromatography on a diode matrix detector with preliminary concentration by solid-phase extraction

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Abstract

Introduction. Antibiotic contamination of the environment is a serious environmental threat that poses a hazard to human health. To monitor the content of tetracycline antibiotics in environmental objects and control technological processes aimed at their disposal, accessible analytical methods are needed.

Purpose of the study. Development of a method for determining antibiotics of the tetracycline group in water using a diode array detector with preliminary solid-phase concentration.

Material and methods. The objects of the study were model solutions of minocycline, tetracycline, oxytetracycline, demeclocycline, metacycline, and doxycycline in deionized, tap, natural, and treated wastewater. For solid-phase extraction, Diapak P and Diapak PG cartridges were used. SPE was performed using a VacMaster-10 manifold (Biotage). Chromatographic separation was carried out on Diasphere C10CN and Kromasil Eternity 250 × 4.6 mm 5 µm columns on an Agilent 1100 liquid chromatograph (Agilent Technology).

Results. Optimal conditions for the chromatographic separation of minocycline, tetracycline, oxytetracycline, demeclocycline, metacycline, and doxycycline were selected: isocratic mode, wavelength of 350 nm, mobile phase — acetonitrile: aqueous solution of phosphoric acid (pH = 3.0). The analysis time on Diasphere C10CN and Kromasil Eternity columns was 12 and 14 minutes, respectively. The reliability of the linear approximation in both cases was more than 0.99, however, the slopes on the Kromasil Eternity column were 1.35–1.65 times higher than on Diasphere C10CN. The degree of extraction of tetracyclines from deionized water on Diapak P and Diapak PG cartridges was 90–95%, from tap water 61–89%, from purified waste water: 51–87%.

Limitations. The method is not suitable for water bodies with tetracycline contents less than 2 µg/dm3.

Conclusion. An HPLC method has been developed for the determination of minocycline, tetracycline, oxytetracycline, demeclocycline, metacycline, and doxycycline in water with preliminary SPE concentration on Diapak P and Diapak PG cartridges. The lower limit of determination for the sorption of target compounds from 0,1 dm3 of sample was 2 µg/dm3.

Compliance with ethical standards. The study does not require the conclusion of the Biomedical Ethics Committee.

Contribution:
Nekrasova L.P. — the concept and design of the study, writing the text, collecting material and processing data, editing;
Kuleshova O.Yu. — collecting material and processing data.
All authors — approval of the final version of the article, responsibility for the integrity of all parts of the article.

Conflict of interest. The authors declare no conflict of interest.

Acknowledgment. The study was supported by the state contract “Conducting an analytical review to identify priority chemical pollutants in the wastewater of the metropolis and water bodies polluted by them.”

Received: October 19, 2023 / Revised: February 14, 2024 / Accepted: March 11, 2024 / Published: April 10, 2024

About the authors

Larisa P. Nekrasova

Centre for Strategic Planning and Management of Biomedical Health Risks of the FMBA

Author for correspondence.
Email: LNekrasova@cspmz.ru
ORCID iD: 0000-0002-1269-3161

MD, PhD, Head of the Hygiene Department, of the Centre for Strategic Planning and Management of Biomedical Health Risks of the FMBA, Moscow, 119121, Russian Federation

e-mail: LNekrasova@cspmz.ru

Russian Federation

Oksana Ju. Kuleshova

Centre for Strategic Planning and Management of Biomedical Health Risks of the FMBA

Email: OKuleshova@cspmz.ru

MD, PhD, DSci., Leading Researcher of the Department of Physical and Chemical Research and Ecotoxicology of the Centre for Strategic Planning and Management of Biomedical Health Risks of the FMBA, Moscow, 119121, Russian Federation

e-mail: OKuleshova@cspmz.ru

Russian Federation

References

  1. Timofeeva S.S., Gudilova O.S. Antibiotics in the environment: status and problems. Tekhnosfernaya bezopasnost’. 2021; 6(3): 251–65. https://doi.org/10.21285/2500-1582-2021-3-251-265 https://elibrary.ru/diorqu (in Russian)
  2. Felisa E., Kalka J., Sochackia A., Kowalskaa K., Bajkacz S., Harnisz M., et al. Antimicrobial pharmaceuticals in the aquatic environment – occurrence and environmental implications. Eur. J. Pharmacol. 2020; 866: 172813. https://doi.org/10.1016/j.ejphar.2019.172813
  3. Du L., Liu W. Occurrence, fate, and ecotoxicity of antibiotics in agroecosystems. A review. Agron. Sustain. Dev. 2012; (32): 309–27. https://doi.org/10.1007/s13593-011-0062-9
  4. Mojica E.R.E., Aga D.S. Antibiotics pollution in soil and water: Potential ecological and human health issues. In: Nriagu J.O., ed. Encyclopedia of Environmental Health. Elsevier; 2011: 97–110. https://doi.org/10.1016/B978-0-444-52272-6.00338-X
  5. Rodriguez-Mozaza S., Vaz-Moreirac I., Della Giustinaa S.V., Llorcaa M., Barcelóa D., Schuberte S., et al. Antibiotic residues in final effluents of European wastewater treatment plants and their impact on the aquatic environment. Environ. Int. 2020; 140: 105733. https://doi.org/10.1016/j.envint.2020.105733
  6. Prozherina Yu. Pharmaceutical waste as a new environmental issue. Remedium. 2017; (11): 14–9. https://doi.org/10.21518/1561-5936-2017-11-14-19 https://elibrary.ru/zwhrqh (in Russian)
  7. Terekhova V.A., Rudneva I.I., Poromov A.A., Paramonova A.I., Kydralieva K.A. Distribution and biological effects of antibiotics Inwater ecosystems (review). Voda: Khimiya i ekologiya. 2019; (3–6): 92–112. https://elibrary.ru/cimplw (in Russian)
  8. Namazova-Baranova L.S., Baranov A.A. Antibiotic resistance in modern world. Pediatricheskaya farmakologiya. 2017; 14(5): 341–54. https://doi.org/10.15690/pf.v14i5.1782 https://elibrary.ru/ztiett (in Russian)
  9. Khmelevtsova L.E., Sazykin I.S., Azhogina T.A., Sazykina M.A. The dissemination of antibiotic resistance in various environmental objects (Russia). Environ. Sci. Pollut. Res. 2020; 27(35): 43569–81. https://doi.org/10.1007/s11356-020-10231-2
  10. Duarte A.C., Rodrigues S., Afonso A., Nogueira A., Coutinho P. Antibiotic resistance in the drinking water: old and new strategies to remove antibiotics, resistant bacteria, and resistance genes. Pharmaceuticals (Basel). 2022; 15(4): 393. https://doi.org/10.3390/ph15040393
  11. Antropova N.S., Ushakova O.V., Vodyanova M.A., Savostikova O.N. Risk of antibiotic resistance extension via environmental objects and food products (review). Rossiyskiy zhurnal vosstanovitel’noy meditsiny. 2020; (4): 36–51. https://elibrary.ru/eqyxxj (in Russian)
  12. Wang J., Ye K.X., Tian Y., Liu K., Liang L.L., Li Q.Q., et al. Simultaneous determination of 22 antibiotics in environmental water samples by solid phase extraction-high performance liquid chromatography-tandem mass spectrometry. Se Pu. 2023; 41(3): 241–9. https://doi.org/10.3724/sp.j.1123.2022.06004 (in Chinese)
  13. Ferrer I., Zweigenbaum J.A., Thurman E.M. Analysis of 70 Environmental Protection Agency priority pharmaceuticals in water by EPA Method 1694. J. Chromatogr. A. 2010; 1217(36): 5674–86. https://doi.org/10.1016/j.chroma.2010.07.002
  14. Kim C., Ryu H.D., Chung E.G., Kim Y., Rhew D.H. Determination of veterinary antibiotic residues: IV. Comparable analytical methods with EPA methods 1694. J. Korean Soc. Water Environ. 2016; 32(6): 670–99. https://doi.org/10.15681/KSWE.2016.32.6.670
  15. Pailler J.Y., Krein A., Pfister L., Hoffmann L., Guignard C. Solid phase extraction coupled to liquid chromatography-tandem mass spectrometry analysis of sulfonamides, tetracyclines, analgesics and hormones in surface water and wastewater in Luxembourg. Sci. Total. Environ. 2009; 407(16): 4736–43. https://doi.org/10.1016/j.scitotenv.2009.04.042
  16. Kozlova M.A., Gal’vidis I.A., Burkin M.A. Features of pharmaceutical pollution of water bodies-sources of drinking water supply in Moscow (a case study for some antibiotics). Meteorologiya i gidrologiya. 2020; (8): 87–91. https://elibrary.ru/iqjwtd (in Russian)
  17. Nekrasova L., Russkikh Ya., Chernova E., Zhakovskaya Z., Nikiforov V. Simultaneous determination some pharmaceuticals using liquid chromatography-high resolution mass spectrometer LTQ orbitrap. Analitika. 2012; (2): 38–44. https://elibrary.ru/piespt (in Russian)
  18. Savostikova O.N., Nekrasova L.P., Alekseeva A.V., Mamonov R.A. Study of the chemical composition of metropolis wastewater. In: Sytin Readings – 2020. Proceedings of the First National Congress with International participation on Human Ecology, Hygiene and Environmental Medicine [Sysinskie chteniya – 2020. Materialy I Natsional’nogo kongressa s mezhdunarodnym uchastiem po ekologii cheloveka, gigiene i meditsine okruzhayushchey sredy]. Moscow; 2020: 304–6. https://elibrary.ru/binivj (in Russian)
  19. Lyu J., Chen Y., Zhang L. Antibiotics in drinking water and health risks – China, 2017. China CDC Wkly. 2020; 2(23): 413–7. https://doi.org/10.46234/ccdcw2020.106
  20. Wang H., Wang N., Wang B., Zhao Q., Fang H., Fu C., et al. Antibiotics in drinking water in Shanghai and their contribution to antibiotic exposure of school children. Environ. Sci. Technol. 2016; 50(5): 2692–9. https://doi.org/10.1021/acs.est.5b05749
  21. Ansam R. Mahmood, Halah H. Al-Haideri and Fikrat M. Hassan. Detection of Antibiotics in Drinking Water Treatment Plants in Baghdad City, Iraq. Advances in Public Health Volume 2019, Article ID 7851354, 10 pages https://doi.org/10.1155/2019/7851354
  22. Krasnova T.A., Amelin V.G. Identification and detection of antibiotics in drinking water using mass spectrometry with matrix-assisted laser desorption/ionization. Voda: khimiya i ekologiya. 2013; (11): 81–7. https://elibrary.ru/rpqguz (in Russian)
  23. Udalova A.Yu., Dmitrienko S.G., Apyari V.V. Methods for the separation, preconcentration, and determination of tetracycline antibiotics. Zhurnal analiticheskoy khimii. 2015; 70(6): 577–93. https://doi.org/10.1134/S1061934815060180 https://elibrary.ru/ugblvf (in Russian)
  24. Gray A.D., Todd D., Hershey A.E. The seasonal distribution and concentration of antibiotics in rural streams and drinking wells in the piedmont of North Carolina. Science of the Total Environment. 2020. 710, 136286. https://doi.org/10.1016/j.scitotenv.2019.136286
  25. Lavrukhina O.I., Amelin V.G., Kish L.K., Tret’yakov A.V., Pen’kov T.D. Determination of residual amounts of antibiotics in environmental objects and food products. Zhurnal analiticheskoy khimii. 2022; 77(11): 969–1015. https://doi.org/10.31857/S004445022211007X https://elibrary.ru/ehjxdo (in Russian)
  26. Mutavdzić Pavlović D., Babić S., Dolar D., Asperger D., Kosutić K., Horvat A.J., et al. Development and optimization of the SPE procedure for determination of pharmaceuticals in water samples by HPLC-diode array detection. J. Sep. Sci. 2010; 33(2): 258–67. https://doi.org/10.1002/jssc.200900571
  27. Udalova A.Yu., Dmitrienko S.G., Natchuk S.V., Apyari V.V., Zolotov Yu.A. Preconcentration of tetracycline antibiotics on a hyper-crosslinked polystyrene and their determination in waters by high-performance liquid chromatography. Zhurnal analiticheskoy khimii. 2015; 70(3): 273–8. https://doi.org/10.1134/S1061934815030211 https://elibrary.ru/ufnabp
  28. Melekhin A.O., Tolmacheva V.V., Shubina E.G., Dmitrienko S.G., Apyari V.V., Grudev A.I. Using hypercrosslinked polystyrene for the multicomponent solid-phase extraction of residues of 63 veterinary preparations in their determination in chicken meat by high-performance liquid chromatography-tandem mass spectrometry. Zhurnal analiticheskoy khimii. 2021; 76(8): 946–59. https://doi.org/10.1134/S1061934821060046 https://elibrary.ru/grljlh
  29. Eksperiandova L.P., Belikov K.N., Khimchenko S.V., Blank T.A. Once Again about Determination and Detection Limits. Zhurnal analiticheskoy khimii. 2010; 65 (3): 229–34. https://elibrary.ru/ kkilqd
  30. EPA Method 1694: Pharmaceuticals and Personal Care Products in Water, Soil, Sediment, and Biosolids by HPLC/MS/MS. U.S. Environmental Protection Agency Office of Water; 2007. Available at: https://www.epa.gov/sites/default/files/2015-10/documents/method_1694_2007.pdf
  31. Pulicharla R., Hegde K., Brar S.K., Surampalli R.Y. Tetracyclines metal complexation: Significance and fate of mutual existence in the environment. Environ. Pollut. 2017; 221: 1–14. https://doi.org/10.1016/j.envpol.2016.12.017

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